Pesticidal oxadiazines

ABSTRACT

Compounds of the formula ##STR1## wherein: Z is ##STR2## wherein x is an integer from 0 to 4, n is an integer from 0 to 5 and R is defined below; or ##STR3## wherein n is an integer from 0 to 5 and R is defined below; R is selected from the group consisting of: hydrogen; C 1  -C 4  alkyl; C 1  -C 4  alkoxy; halogen; nitro; phenyl; cyano; phenoxy; benzyloxy; benzyl; C 1  -C 4  dialkylamino; C 1  -C 4  alkylthio; or C 1  -C 4  haloalkyl; and 
     R 1  is a C 1  -C 4  haloalkyl other than a chloroalkyl, or a group of the formula ##STR4## wherein R 4  is halogen, C 1  -C 4  haloalkyl or C 1  -C 4  haloalkoxy; physiologically acceptable salts thereof. These compounds exhibit insecticidal and acaricidal activity.

This is a continuation-in-part of U.S. application Ser. No. 07/942,705,filed on Sep. 9, 1992, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention is directed to substituted oxadiazines, which compoundsexhibit unexpectedly desirable activity as pesticides, including asinsecticides and acaricides. In other aspects, this invention isdirected to pesticidal compositions comprising such compounds as well asto methods of controlling pests employing such compounds and/orcompositions.

The destruction by acarids and insects presents a serious problem toagriculture. A wide variety of field crops are in need of protectionfrom acarids and/or insects including such valuable crops as soybeans,corn, peanuts, cotton, alfalfa and tobacco. In addition, vegetables suchas tomatoes, potatoes, peas, sugarbeet, carrots and the like, as well asfruits, nuts, ornamentals and seed bed crops such as apples, peaches,citrus fruit, almonds and grapes may also require protection from theravages of such pests.

2. Description of Related Art

J. Med. Chem, 1966, 753-758 refers to various 2-substituted4H-1,3,4-oxadiazines said to have anticonvulsant activity in mice. U.S.Pat. No. 3,420,826 refers to certain 2,4,6-substituted4H-1,3,4-oxadiazines, said to have utility as sedatives,anticonvulsants, and as pesticides, specifically against nematodes,plants, and fungi. U.S. Pat. No. 3,420,825 refers to methods forproducing those compounds.

SUMMARY OF THE INVENTION

In one aspect, the present invention is directed to compounds having theformula: ##STR5## wherein: Z is ##STR6## wherein x is an integer from 0to 4, n is an integer from 0 to 5 and R is defined below; or ##STR7##wherein n is an integer from 0 to 5 and R is defined below;

R is selected from the group consisting of: hydrogen; C₁ -C₄ alkyl; C₁-C₄ alkoxy; halogen; nitro; phenyl; cyano; phenoxy; benzyloxy; benzyl;C₁ -C₄ dialkylamino; C₁ -C₄ alkylthio; or C₁ -C₄ haloalkyl; and

R¹ is a C₁ -C₄ haloalkyl other than a chloroalkyl, preferably a C₁ -C₄fluoroalkyl, or a group of the formula ##STR8## wherein R⁴ is hydrogen,halogen, C₁ -C₄ haloalkyl or C₁ -C₄ haloalkoxy, preferably a group ofthe formula ##STR9## wherein R⁴ is halogen, C₁ -C₄ fluoroalkyl or C₁ -C₄fluroralkoxy, more preferably --Cl, --CF₃ or --OCF₃ ; andphysiologically acceptable salts thereof.

The compositions of this invention are comprised of (A) one or morecompounds having the structure of formula I above, and (B) a suitablecarrier. Such suitable carriers may be solid or liquid in nature. Thecompounds and compositions of the present invention exhibit pesticidalactivity, especially against insects and acarids.

DETAILED DESCRIPTION OF THE INVENTION

The compounds of this invention can be prepared by reacting a hydrazideof formula (III) below ##STR10## where R has the meanings describedabove, with 1-bromo-2-fluoroethane in the presence of a base. Such basesinclude alkali metal hydroxides. Preferred bases include sodium orpotassium hydroxide.

The compositions of the present invention may be prepared by formulatingone or more compounds of the present invention with a suitable carrier,such as a liquid or solid carrier.

Suitable liquid carriers may be comprised of water, alcohols, ketones,phenols, toluene and xylenes. In such formulations, additivesconventionally employed in the art may be utilized, such as one or moresurface active agents and/or inert diluents, to facilitate handling andapplication of the resulting pesticide composition.

Alternatively, the pesticidal compounds may be applied in liquid orsprays when utilized in a liquid carrier, such as in a solutioncomprising a compatible solvent such as acetone, benzene, toluene orkerosene, or as dispersed in a suitable non-solvent medium such aswater.

The pesticidal compositions may alternatively comprise solid carrierstaking the form of dusts, granules, wettable powders, pastes, aerosols,emulsions, emulsifiable concentrates, and water-soluble solids. Forexample, the pesticidal compounds of this invention may be applied asdusts when admixed with or absorbed onto powdered solid carriers, suchas mineral silicates, e.g., mica, talc, pyrophyllite and clays, togetherwith a surface-active dispersing agent so that a wettable powder isobtained which then is applied directly to the loci to be treated.Alternatively, the powdered solid carrier containing the compoundadmixed therewith may be dispersed in water to form a suspension forapplication in such form.

Granular formulations of the compounds are preferred for field treatmentand are suitable for application by broadcasting, side dressing, soilincorporation or seed treatment, and are suitably prepared using agranular or pellitized form of carrier such as granular clays,vermiculite, charcoal or corn cobs. The pesticide is dissolved in asolvent and sprayed onto an inert mineral carrier such as attapulgitegranules (10-100 mesh), and the solvent is then evaporated. Suchgranular compositions may contain from 2-25% pesticide based on carrierplus pesticide, with 3-15% being preferred. In addition, the pesticidemay also be incorporated into a polymeric carrier such as polyethylene,polypropylene, butadiene-styrene, styrene-acryonitrile resins,polyamides, poly(vinyl acetates) and the like. When encapsulated, thepesticide may advantageously be released over an even longer timeperiod, extending its effectiveness further than when used innon-encapsulated form.

Another method of application to loci to be treated is aerosoltreatment, for which the compound may be dissolved in an aerosol carrierwhich is a liquid under pressure but which is a gas at ordinarytemperature (e.g., 20° C.) and atmospheric pressure. Aerosolformulations may also be prepared by first dissolving the compound in aless volatile solvent and then admixing the resulting solution with ahighly volatile liquid aerosol carrier.

For pesticidal treatment of plants (such term including plant parts),the compounds of the invention preferably are applied in aqueousemulsions containing a surface-active dispersing agent which may benon-ionic, cationic or anionic. Suitable surface-active agents are wellknown in the art, and include those disclosed in U.S. Pat. No. 2,547,724(columns 3 and 4). The compounds of the invention may be mixed with suchsurface-active dispersing agents, with or without an organic solvent, asconcentrates for the subsequent addition of water to yield aqueoussuspensions of the compounds at desired concentration levels.

In addition, the compounds may be employed with carriers whichthemselves are pesticidally active, such as insecticides, acaricides,fungicides or bactericides.

It will be understood that the amount of the pesticidally activecompound in a given formulation will depend upon the specific pest to becombatted, as well as upon the specific chemical composition andformulation of the compound being employed, the method of applying thecompound/formulation and the locus of treatment so that the pesticidallyeffective amount of the compound may vary widely. Generally, however,concentrations of the compound as the active ingredient in pesticidallyeffective formulations may range from about 0.1 to about 95 percent byweight. Spray dilutions may be as low as a few parts per million, whileat the opposite extreme, full strength concentrates of the compound maybe usefully applied by ultra low volume techniques. When plantsconstitute the loci of treatment, concentration per unit area may rangebetween about 0.01 and about 50 pounds per acre, with concentrations ofbetween about 0.1 and about 10 pounds per acre preferably being employedfor crops such as corn, tobacco, rice and the like.

To combat pests, sprays of the compounds may be applied to any suitablelocus, such as to the pests directly and/or to plants upon which theyfeed or nest. The pesticidally active formulations may also be appliedto the soil or other medium in which the pests are present. Harmfulinsects and acarids attack a wide variety of plants, including bothornamental and agricultural plants and inflict damage by consuming rootsand/or foliage, withdrawing vital juices from the plants, secretingtoxins and often by transmitting diseases. The compounds of the presentinvention may be advantageously utilized to minimize or prevent suchdamage. The specific methods of application, as well as the selectionand concentration of these compounds will of course vary depending uponsuch circumstances as geographic area, climate, topography, planttolerance, etc. For specific circumstances, one skilled in the art mayreadily determine the proper compound, concentration and method ofapplication by routine experimentation.

The compounds of the invention are particularly useful as insecticidesand acaricides for foliar application. The compounds are particularlyeffective for controlling insects, such as tobacco budworm and mites,such as spider mites and rust mites.

The following examples are given merely to illustrate the scope of thepresent invention. The invention herein is not intended to be limited tothe actual examples provided.

EXAMPLE 1 Preparation of 2-(4-Bromophenyl)-4H-1,3,4-Oxadiazine

A solution of 2.9 g (0.07 mole) sodium hydroxide dissolved in 10 ml ofwater was added dropwise at room temperature to a mixture of 6.5 g (0.03mole) 4-bromobenzoic hydrazide and 4.0 g (0.03 mole)1-bromo-2-fluoroethane in 25 ml of ethanol. The resulting solution wasrefluxed for two and one-half hours. The mixture was cooled to roomtemperature, diluted with 150 ml of water and extracted several timeswith ether (100 ml). After separation and drying over anhydrous sodiumsulfate, the solution was filtered and evaporated under reduced pressureleaving 4.6 grams of an oil (63.6% yield), which was purified bydistillation. The product was characterized by IR and NMR spectroscopy.

EXAMPLE 1A Preparation of2-(4-bromophenyl)-5,6-dihydro-N-[(4-trifluoromethyl)phenyl]-4H-1,3,4-oxadiazine-4-carbamide(Compound 70)

To 1 gm of 2-(4-bromophenyl)-5,6-dihydro-4H-1,3,4-oxadiazine dissolvedin 40 ml of acetonitrile, was added, with stirring, 2 drops oftriethylamine followed by 1 gm of 4-(trifluoromethyl)phenyl isocyanateand stirred for 1 hour at room temperature. The solvent was thenevaporated under reduced pressure and the resulting solid was washedwith hexane and air-dried, producing 1.0 gm of2-(4-bromophenyl)-5,6-dihydro-N-[(4-trifluoromethyl)phenyl]-4H-1,3,4-oxadiazine-4-carbamide,mp 146°-148° C. (50% yield).

Additional compounds were prepared in accordance with the aboveprocedures. These compounds and their acaricidal and insecticidalactivity are summarized in Tables I and II. The NMR data are summarizedin Table III.

                                      TABLE I                                     __________________________________________________________________________     ##STR11##                                                                    CMPD #                                                                              R      X   R.sup.1 MI  MIOVL                                                                              RPH                                                                              TB TBOV                                  __________________________________________________________________________    1     2-F    --  H       0    70(0)                                                                             50 40  100                                  2     H      CH.sub.2                                                                          H       0   100(0)                                                                             50 20   0                                   3     H      --  CONHC.sub.6 H.sub.4 Cl                                                                0   100(0)                                                                             30 0    0                                   4     4-CH.sub.3                                                                           --  CH.sub.3                                                                              0    40(0)                                                                             80 0    0                                   5     4-CH.sub.3 O                                                                         --  H       0   0    100                                                                              80  100                                  6     4-CH.sub.3 O                                                                         --  COHNC.sub.6 H.sub.4 Cl                                                                0    70(L)                                                                             100                                                                              40  100                                  7     4-F    --  H       100  50(L)                                                                             90 80   89                                  8     2,4-Cl CH.sub.2 O                                                                        H       0   0    100                                                                              40   99                                  9     2,4-Cl CH.sub.2 O                                                                        CONHC.sub.6 H.sub. 5                                                                  0    70(L)                                                                             100                                                                              0    56                                  10    2,5-Cl --  H       70  100(0)                                                                             100                                                                              80  100                                  11    4-Cl   --  H       0    70(0)                                                                             50 80  100                                  12    4-CH.sub.3                                                                           --  H       0   0    100                                                                              100 100                                  13    4-CH.sub.3 S                                                                         --  CH.sub.3                                                                              0    50(0)                                                                             25 0   100                                  14    4-CH.sub.3 S                                                                         --  H       50  100(0)                                                                             50 0    8                                   15    4-CH.sub.3 S                                                                         --  CONHC.sub.6 H.sub.4 Cl                                                                50  100(0)                                                                              0 0   100                                  16    4-Br   --  H       0   100(0)                                                                             75 0   100                                  17    4-NO.sub.2                                                                           --  H       0   100(0)                                                                             90 0   100                                  18    4-Br   --  CONHC.sub.6 H.sub.4 Cl                                                                0   100(0)                                                                             50 60  100                                  19    2,4-CH.sub.3                                                                         --  H       0   100(0)                                                                             50 0    97                                  20    2,4-CH.sub.3                                                                         --  CONHC.sub.6 H.sub.4 Cl                                                                0   100(0)                                                                              0 0   100                                  21    2,4-CH.sub.3                                                                         --  CON(CH.sub.3).sub.2                                                                   0   100(0)                                                                             25 0   100                                  22    2-C.sub.6 H.sub.5 CH.sub.2 O                                                         --  H       0    80(0)                                                                             95 55  100                                  23    2-Cl   --  CONHC.sub.6 H.sub.4 Cl                                                                0   100(0)                                                                              0 0    6                                   24    2-Cl   --  H       0   100(0)                                                                             50 10  100                                  25    4-CF.sub.3                                                                           --  H       0   100(0)                                                                              0 100 100                                  26    4-CF.sub.3                                                                           --  CONHC.sub.6 H.sub.4 Cl                                                                0   100(0)                                                                              0 100 100                                  27    2-C.sub.6 H.sub.5 CH.sub.2 O                                                         --  CONHC.sub.6 H.sub.4 Cl                                                                50   70(0)                                                                             45 32   48                                  28    2,4-CH.sub.3                                                                         --  CH.sub.3                                                                              0    70(0)                                                                             25 20   99                                  29    2,4-Cl --  H       100 100(0)                                                                             100                                                                              20  100                                  30    2-CH.sub.3                                                                           --  H       0    70(0)                                                                             90 0    98                                  31    2,4-Cl --  CONHC.sub.6 H.sub.4 Cl                                                                0   0    100                                                                              0   100                                  32    3-Br   --  H       50  100(0)                                                                             100                                                                              0   100                                  33    3-Br   --  CONHCH.sub.3                                                                          50  100(0)                                                                             100                                                                              40  100                                  34    2-C.sub.6 H.sub.5 O                                                                  --  H       0    50(0)                                                                             100                                                                              0    39                                  35    4-C.sub.2 H.sub.5 O                                                                  --  H       0    80(0)                                                                             95 0   100                                  36    3-CH.sub.3 O                                                                         --  H       0   100(0)                                                                             100                                                                              20  100                                  37    4-C.sub. 6 H.sub.5                                                                   --  H       0    85(0)                                                                             100                                                                              80  100                                  38    2-CH.sub.3 O                                                                         --  H       0    70(0)                                                                             60 0    0                                   39    3,4-CH.sub.3 O                                                                       --  H       0    50(0)                                                                             95 0    11                                  40    4-N(CH.sub.3).sub.2                                                                  --  H       0   100(0)                                                                             95 0   100                                  41    4-C(CH.sub.3).sub.3                                                                  --  H       0    50(0)                                                                             90 0    98                                  42    3-CH.sub.3                                                                           --  H       0   100(0)                                                                             100                                                                              40   98                                  43    3,4-CH.sub.3 O                                                                       CH.sub.3                                                                          H       0    50(0)                                                                             60 0    1                                   44    3-F    --  H       0   100(0)                                                                             75 20  100                                  45    2-Cl, 4-NO.sub.2                                                                     --  H       0   100(0)                                                                             100                                                                              0   100                                  46    2-CH.sub.3, 4-Cl                                                                     CH.sub.2 O                                                                        H       0   100(0)                                                                             99 20  100                                  47    4-F    CH.sub.2 O                                                                        H       0   100(0)                                                                             100                                                                              60  100                                  48    4-CH.sub.3 O                                                                         (CH.sub.2).sub.2                                                                  H       0   100(0)                                                                             30 0    95                                  49    H      (CH.sub.2).sub.2                                                                  H       0   100(0)                                                                             50 0   100                                  50    4-Cl   CH.sub.2 O                                                                        H       0   100(0)                                                                             95 4    93                                  51    H      CH.sub.2 O                                                                        H       0    70(0)                                                                             90 0   100                                  __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________     ##STR12##                                                                    CMPD #                                                                              R.sup.3   R.sup.2    MI MIOVL                                                                              RPH TB  TBOV                               __________________________________________________________________________    52    C.sub.4 H.sub.3 O                                                                       CH.sub.3   0  0    85  0   0                                  53    CH.sub.2C.sub.10 H.sub.7                                                                CH.sub.3   0  0    75  0   1                                  54    CH.sub.2C.sub.5 H.sub.4 N                                                               CH.sub.3   0  0    75  0   0                                  55    CH.sub.2C.sub.8 H.sub.6 N                                                               H          0  0    100 0   0                                  56    3-BrC.sub.6 H.sub.4                                                                     H.HCl      0  50(0)                                                                              100 0   2                                  57    C.sub.6 H.sub.4N(CH.sub.3).sub.2                                                        H.HCl      0  50(0)                                                                              100 0   0                                  58    C.sub.6 H.sub.44-OC.sub.2 H.sub.5                                                       H.HCl      0  85(0)                                                                              100 0   100                                59    C.sub.6 H.sub.32,3-(CH.sub.3 O).sub.2                                                   H.HCl      0  80(0)                                                                              95  20  21                                 60    C.sub.6 H.sub.44-C(CH.sub.3).sub.3                                                      H.HCl      0  0    95  0   0                                  61    C.sub.6 H.sub.43-CH.sub.3 O                                                             H.HCl      0  0    100 0   0                                  62    CH.sub.3  H          0  0    90  0   0                                  63    C.sub.5 H.sub.4 N                                                                       H          0  50(0)                                                                              25  40  0                                  64    CH.sub.2C.sub.4 H.sub.3 S                                                               H          0  100(0)                                                                             90  0   9                                  65    4-BrC.sub.6 H.sub.4                                                                     H.HCl      0  100(0)                                                                             40  40  100                                66    C.sub.3 H.sub.7                                                                         H          0  0    50  16  7                                  67    4-BrC.sub.6 H.sub.4                                                                     CH.sub.2 CH.sub.2 F.HCl                                                                  30 100(0)                                                                             85  100 100                                68    C.sub.4 H.sub.3 N.sub.2                                                                 H          0  100(0)                                                                             70  15  0                                  69    4-BrC.sub.6 H.sub.4                                                                     CONHC.sub.6 H.sub.4 -4-OCF.sub.3                                                         0  0     0  100 5                                  70    4-BrC.sub.6 H.sub.4                                                                     CONHC.sub.6 H.sub.4 -4-CF.sub.3                                                          30 0     0  100 1                                  __________________________________________________________________________

                  TABLE III                                                       ______________________________________                                        01       m(2)2.3; m(2)4.5; m(5)7.3-7.8                                        02       m(2)3.0; s(2)3.4; m(2)4.3; s(5)7.3                                   03       m(2)4.0; m(2)4.5; m(9)7.3-8.1; s(1)9.2                               04       s(3)2.3; m(4)7.1-7.7; s(3)2.9; m(2)3.1; m(2)4.5                      05       m(2)3.1; s(3)3.8; m(2)4.5; d(2)6.9;d(2)7.7                           06       m(2)3.1; s(3)3.7; m(2)4.3; m(8)6.9-7.7                               07       m(2)3.1; m(24.5; m(5)7.2-8.0                                         08       m(2)3.0; m(2)4.2; s(2)4.6; m(4)7.0-7.4                               09       m(2)3.0; m(2)4.2; s(2)4.6; m(7)7.0-7.5                               10       m(2)3.2; m(2)4.5; s(2)7.3; S(1)7.5                                   11       m(2)3.2; m(2)4.5; m(5)7.3-7.9                                        12       s(3)2.3; m(2)3.1; m(2) 4.5; d(2)7.2; d(2)7.7                         13       s(3)2.4; s(3)2.8; m(2)3.0; m(2)4.4; m(4)7.1-7.7                      14       s(3)2.5; m(2)3.2; m(2)4.5; d(2)7.2; d(2)7.6                          15       s(3)2.5; s(1)8.8; m(2)3.0; m(2)4.4; m(4)7.1-7.7                      16       m(2)3.1; m(2)4.5; m(5)7.5                                            17       m(2)3.1; m(2)4.5; m(5)8.0                                            18       m(2)3.1; m(2)4.4; m(8)7.0-7.7                                        19       s(3)2.3; s(3)2.4; m(2)3.1; m(2)4.5; m(4)6.8-7.4                      20       s(3)2.3; s(3)2.4; m(2)3.0; m(2)4.4; m(7)7.0-7.5;                              s(1)8.7                                                              21       s(3)2.3; s(3)2.4; s(6)3.0; m(2)3.0; m(2)4.4;                                  m(3)6.9-7.4                                                          22       m(2)3.1; m(2)4.5; s(2)5.0; m(10)6.8-7.5                              23       m(2)3.0; m(2)4.4; m(8)7.0-7.6                                        24       m(2)3.1; m(2)4.5; m(5) 7.1-7.5                                       25       m(2)3.1; m(2)4.5; m(5)7.4-7.9                                        26       m(2)3.1; m(2)4.4; m(8)7.0-7.8                                        27       m(2)3.0; m(2)4.4; s(2)5.0; m(14)7.0-7.5                              28       s(3)2.3; s(3)2.4; s(3)2.8; m(2)3.0; m(2)4.5                                   m(3)7.0-7.3                                                          29       m(2)3.1; m(2)4.5; m(4)7.1-7.6                                        30       s(3)2.4; m(2)3.1; m(2)4.5; m(5) 7.1-7.6                              31       m(2)4.0; m(2)4.5; m(7)7.1-7.6; s(1)8.5                               32       m(2)3.1; m(2)4.5; m(4)7.2-7.9                                        33       d(3)2.9; m(2)3.1; m(2)4.4; m(4)7.1-7.9                               34       m(2)3.0; m(2)4.3; m(9)7.0-7.5                                        35       t(3)1.4; m(2)3.0; q(2)4.0; m(2)4.5; m(2)6.9;                                  m(2)7.8                                                              36       m(2)3.0; s(3)3.8; m(2)4.5; m(4)6.9-7.4                               37       m(2)3.0; m(2)4.5; m(9)7.2-7.9                                        38       m(2)3.0; s(3)3.8; m(2)4.4; m(4)6.9-7.4                               39       m(2)3.0; s(6)4.0; m(2)4.4; m(3)6.8-7.3                               40       s(6)3.0; m(2)3.0; m(2)4.4; m(4)6.8-7.8                               41       s(9)1.3; m(2)3.0; m(2)4.4; m(4)7.4-7.8                               42       s(3)2.3; m(2)3.1; m(2)4.5; m(4)7.2-7.6                               43       m(2)3.0; s(2)3.5; s(6)3.9; m(2)4.3; s(3)6.9                          44       m(2)3.0; m(2)4.4; m(4)7.0-7.6                                        45       m(2)3.1; m(2)4.4; m(3)7.6-8.1                                        46       s(3)2.1; m(2)3.0; m(2)4.3; s(2)4.5; m(3)7.0-7.2                      47       m(2)3.0; m(2)4.3; s(2)4.4; m(4)6.9-7.1                               48       m(6)2.7-3.0; s(3)3.7; m(2)4.2-4.4; m(4)6.8-7.2                       49       m(6)2.5-3.0; m(2)4.1-4.4; s(5)7.2                                    50       m(2)2.8-3.2; m(4)4.2-4.5; m(4)6.8-7.3                                51       m(2)2.9-3.2; m(4)4.3-4.5; m(5)6.9-7.3                                52       s(3)2.9; m(2)3.0; m(2)4.5; m(3)6.5-7.4                               53       s(3)2.7; m(2)3.1; 3(2)4.0; m(2)4.3; m(7)7.3-8.0                      54       S(3)2.8; m(2)2.9; s(2)3.7; m(2)4.3; m(5)7.0-7.3                      55       m(2)2.9; s(2)3.8; m(2)4.3; m(5)7.0-7.3                               57       s(6)3.1; m(2)3.1; m(2)4.4; m(4)7.0-7.5                               58       t(3)1.4; m(2)3.0; q(2)4.0; m(2)4.3; m(4)6.8-7.9                      59       m(2)3.0; S(6)4.0; m(2)4.5; m(3)6.9-7.5                               60       s(9)1.3; m(2)3.1; m(2)4.4; m(4)7.2-7.9                               61       m(2)3.1; s(3)3.9; m(2)4.4; m(4)7.1-7.7                               62       s(3)2.0; m(2)3.0; m(2)4.2                                            63       m(2)3.0; m(2)4.5; m(5)7.1-8.8                                        64       m(2)2.9; s(2)3.4; m(2)4.3; m(3)7.0-7.3                               65       m(2)3.5; m(2)4.6; s(4)7.7                                            66       t(3)1.0; m(2)1.4-1.7; m(2)2.0-2.3; m(2)2.9-3.2;                               m(2)4.2-4.5                                                          67       m(4)3.3-3.9; m(4)4.5-5.5; m(4)7.5-7.9                                68       m(2)3.1-3.3; m(2)4.5-4.7; s(2)8.5; s(1)9.1                           69       m(2)3.7-4.0; m(2)4.4-4.7; m(8)7.2-8.2; s(1)9.4                       70       m(2)3.7-4.0; m(2)4.4-4.7; m(8)7.6-8.2; s(1)9.5                       ______________________________________                                    

EXAMPLE 2 Preparation of Formulations

The remaining examples relate to the pesticidal use of the compounds ofthis invention. In all these examples a stock solution for the compoundswere prepared at 3000 ppm by dissolving 0.3 gram of the compound to betested in 10 ml of acetone and adding 90 ml of distilled water plus fourdrops of ethoxylated sorbitan monolaurate, or a similar suitable wettingagent. For each example that follows, this stock solution was used andthe specified dilutions made.

All the tests discussed below, which involved treatment with compoundsof this invention at concentrations of 3000 to 500 ppm were alwaysrepeated with controls, in which the active compound was not provided,to permit a comparison upon which the percent control was calculated.

EXAMPLE 3 Mite Adulticide and Mite Ovicide/Larvicide Tests

One day before treatment, a "FIG. 8" configuration of tree tanglefootwas applied to each of two cowpea primary leaves, one from each of twoplants in a pot. In each figure, the circle nearer the stem wasdesignated for the mite ovicide/larvicide test and the circle furtherfrom the stem was designated for the mite adulticide test.

Groups of adult mites (Tetranychus urticae Koch) were transferred intoovicide circles one day before treatment and the females were allowed todeposit eggs until one hour before treatment when the adults wereremoved. Plants were sprayed to run off with a 1000 ppm solution dilutedfrom the 3000 ppm stock solution.

One day following treatment, groups of approximately 25 adult mites weretransferred into the adulticide rings. Five days later these rings wereexamined for live mites remaining on the leaves. The percent control wasestimated based on the number of mites surviving on the check plants.

Nine days following treatment the ovicide/larvicide rings were examinedfor hatched eggs and living immature mites. The percent control wasestimated based on the number of eggs hatching and immature mitessurviving on the check plants. When the treatment effect was to eggs,control was designated as ovicidal (O); when the treatment effect was toimmatures, control was designated as larvicidal (L).

Results of the mite adulticide (MI) and ovicide/larvicide (MIOVL) testsare presented in Tables I and II.

EXAMPLE 4 Rice Planthopper Foliar Test

The stock solution of 3000 ppm was diluted to 1000 ppm. One potcontaining approximately 20 Mars variety rice seedlings was treated witheach formulation by spraying with a spray atomizer. One day aftertreatment plants were covered with a tubular cage and twenty adult ricedelphacides, Sogatodes orizicola, were transferred into each cage. Fivedays after transferring, counts were made of the surviving planthoppersin each pot and percent control was estimated.

Results of the testing of rice planthoppers (RPH) are presented inTables I and II.

EXAMPLE 5 Tobacco Budworm Test

The stock solution of 3000 ppm was used for this test. For eachcompound, 0.2 ml was pipetted onto the surface of each of 5 diet cells,allowed to spread over the surfaces and air dried for two hours. Then asecond instar Helicoverpa virescens larva was introduced into each cell.After 14 days, the number of living larvae was determined for eachtreatment and percent control, corrected by Abbott's formula, wascalculated.

The results of the testing of tobacco budworms (TB) are given in TablesI and II.

EXAMPLE 6 Tobacco Budworm Ovicide Test

A solution of 1000 ppm was prepared by dissolving 0.015 g of thecompound to be tested in 2 ml of acetone and adding 13 ml of distilledwater plus 1 drop of ethoxylated sorbitan monolaurate. Cheesecloth onwhich budworms had oviposited eggs 1-2 days before treatment was cutinto pieces, each containing 40-80 eggs. These pieces were immersed for1 minute in the solution. After 5 days, the numbers of hatched andunhatched eggs were counted and an adjusted percent control determined.The results are given in Tables I and II.

EXAMPLE 7 Aphid Tests

A solution of 500 ppm was applied by foliar spray to infested hostplants, and an estimated percent control was determined at 5 days aftertreatment. Either green peach aphid (GPA) on tomato or corn leaf aphid(CLA) on barley was evaluated. The results are given below:

                  TABLE IV                                                        ______________________________________                                        APHID TESTS                                                                                    Percent Control                                              Compound No.       GPA    CLA                                                 ______________________________________                                         5                 100                                                         7                 100                                                        10                 100                                                        11                        100                                                 12                  95                                                        17                  98                                                        19                        100                                                 22                  99                                                        24                        100                                                 25                         99                                                 30                        100                                                 ______________________________________                                    

The test results demonstrate surprising and unexpected efficacy of thecompounds of the instant invention as mite adulticides and miteovicide/larvicides. The compositions were also potent in the control ofinsect pests including but not limited to rice planthoppers, tobaccobudworms, and aphids.

It is apparent that various modifications may be made in the formulationand application of the compounds of this invention without departingfrom the inventive concepts as defined in the following claims.

What is claimed is:
 1. A compound having the formula ##STR13## wherein:Z is ##STR14## wherein x is an integer from 0 to 4, n is an integer from0 to 5 and R is defined below; or ##STR15## wherein n is an integer from0 to 5 and R is defined below; R is selected from the group consistingof: hydrogen; C₁ -C₄ alkyl; C₁ -C₄ alkoxy; halogen; nitro; phenyl;cyano; phenoxy; benzyloxy; benzyl; C₁ -C₄ dialkylamino; C₁ -C₄alkylthio; or C₁ -C₄ haloalkyl; andR¹ is a group of the formula##STR16## wherein R⁴ is hydrogen, halogen, C₁ -C₄ haloalkyl or C₁ -C₄haloalkoxy; or physiologically acceptable salts thereof.
 2. A compoundas recited in claim 1 wherein Z is option a); n is 1 or 2; and x is 0.3. A compound as recited in claim 1 wherein R¹ is a compound of theformula ##STR17## wherein R⁴ is halogen, C₁ -C₄ fluoroalkyl or C₁ -C₄fluoroalkoxy.
 4. A compound as recited in claim 3 wherein R⁴ is chloro,trifluoromethyl or trifluoromethoxy.
 5. A compound as recited in claim 3wherein R is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen or C₁ -C₄alkylthio.
 6. A compound as recited in claim 1 which is2-(4bromophenyl)-5,6-dihydro-N-[4-(trifluoromethyl)-phenyl]-H-1,3,4-oxadiazine-4-carbamideor 2-(4-bromo-phenyl)-5,6-dihydro-N-[4-(trifluoromethoxy)phenyl]-4H-1,3,4-oxadiazine-4-carbamide.7. An insecticidal or acaricidal composition comprising:(A) an effectiveamount of a compound as recited in claim 3; and (B) a suitable carrier.8. An insecticidal or acaricidal composition comprising:(A) an effectiveamount of a compound as recited in claim 1; and (B) a suitable carrier.9. An insecticidal or acaricidal composition comprising:(A) an effectiveamount of a compound as recited in claim 8; and (B) a suitable carrier.10. A method for controlling insects or acarids which comprises applyingto a locus to be protected an effective amount of a compound as recitedin claim
 3. 11. A method for controlling insects or acarids whichcomprises applying to a locus to be protected an effective amount of acompound as recited in claim
 1. 12. A method for controlling insects oracarids which comprises applying to a locus to be protected an effectiveamount of a compound as recited in claim 6.